WO2019069491A1 - 塗料及び被覆鋼材 - Google Patents

塗料及び被覆鋼材 Download PDF

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Publication number
WO2019069491A1
WO2019069491A1 PCT/JP2018/015551 JP2018015551W WO2019069491A1 WO 2019069491 A1 WO2019069491 A1 WO 2019069491A1 JP 2018015551 W JP2018015551 W JP 2018015551W WO 2019069491 A1 WO2019069491 A1 WO 2019069491A1
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Prior art keywords
paint
particles
mass
content
steel material
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PCT/JP2018/015551
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English (en)
French (fr)
Japanese (ja)
Inventor
正人 山下
Original Assignee
株式会社京都マテリアルズ
長瀬産業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 株式会社京都マテリアルズ, 長瀬産業株式会社 filed Critical 株式会社京都マテリアルズ
Priority to CN201880064670.6A priority Critical patent/CN111164168A/zh
Priority to US16/651,599 priority patent/US20200255952A1/en
Priority to JP2019506532A priority patent/JP6587775B2/ja
Priority to PCT/JP2018/035127 priority patent/WO2019069722A1/ja
Priority to KR1020207009480A priority patent/KR20200064081A/ko
Priority to EP18864176.5A priority patent/EP3693422A1/en
Publication of WO2019069491A1 publication Critical patent/WO2019069491A1/ja
Priority to JP2019164497A priority patent/JP2020002376A/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/54—Amino amides>
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/103—Anti-corrosive paints containing metal dust containing Al
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C08K2003/3081—Aluminum sulfate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose

Definitions

  • the present invention relates to a paint and a coated steel material. More specifically, the present invention is applied to a steel material, a steel material covered with a rust layer by oxidation and corrosion, or a steel material covered with an organic layer or an inorganic layer (hereinafter, sometimes simply referred to as steel material).
  • the present invention relates to a paint for enhancing corrosion resistance of steel materials, and further relates to a steel material (coated steel material) on which the paint is applied to form a coating film.
  • stainless steel forms a passive film which is an oxide layer having a high environmental barrier property and exhibits high corrosion resistance.
  • stainless steel is expensive and has problems in corrosion resistance such as pitting due to being a high alloy steel, and is inferior in mechanical properties such as strength and toughness as compared with low alloy steel. There are also many limitations when using it for structures and machines because it is also included.
  • the weathering steel obtained by adding a small amount of elements such as P, Cu, Cr and Ni is a rust (protective rust) having protection against corrosion as the corrosion progresses when it is placed outdoors. It is a low alloy steel that can improve the corrosion resistance of the steel in the atmosphere and can reduce the need for anticorrosion treatment work such as painting thereafter.
  • a weathering steel requires a long time of about 10 years or more until protective rust is formed, and floating rust or flow rust such as red rust or yellow rust due to corrosion at an early stage during the above period As a result, there is a problem that not only appearance is not preferable but also significant damage such as thickness reduction due to corrosion occurs.
  • Patent Document 1 proposes a surface treatment method for forming a phosphate coating on a steel material.
  • the coating of the steel surface is mentioned as a general means for securing corrosion resistance of steel materials.
  • the coating can not prevent the progress of the corrosion from the deterioration of the coating film or the defect of the coating film even in a general corrosive environment, but only delays the progress of the corrosion.
  • there is a coating method to cover high corrosion resistance such as zinc rich primer or zinc rich paint using sacrificial corrosion protection by zinc powder, but similarly, the effect can be exhibited for a relatively short period of time.
  • the deterioration of the coating film and the progress of corrosion from coating film defects can not be essentially prevented.
  • Patent Document 2 discloses that the corrosion resistance can be improved by applying an inorganic zinc rich paint to a steel material and applying a solution containing an Mg compound on the surface of a coating film.
  • coated on steel materials is disclosed.
  • the paints disclosed in these are different from the above-mentioned paints which can not prevent the progress of the corrosion from the deterioration of the paint film and the paint film defect.
  • an oxide layer having corrosion resistance is formed at an early stage at the interface between the film and the steel according to the corrosion reaction of the steel after film formation. Corrosion resistance is obtained.
  • the improvement ratio of the improvement of the corrosion resistance to no treatment is at most about 3 times at most, and even if it can be said that it can cope with a general corrosion environment, the acidic environment Or, it could not be said that sufficient corrosion resistance was provided in the severe corrosive environment containing chloride.
  • Such zinc-rich paint is applied to the surface of clean steel obtained by shot blasting, etc., and applied to steel covered with a rust layer due to oxidation and corrosion to achieve high corrosion resistance. Not shown.
  • the oxide layer formed at the interface between the coating and the steel disclosed in Patent Document 3 and Patent Document 4 exhibits high corrosion resistance and can sufficiently cope with a general corrosive environment, but an acidic environment or It can not be said that it can respond sufficiently in the severe corrosive environment containing chloride.
  • the present invention has been made in view of the above circumstances, and is capable of imparting high corrosion resistance to steel materials and the like in an acidic environment or a severe corrosive environment containing chloride, and a coating obtained using the same.
  • the purpose is to provide steel products.
  • the present invention provides a paint comprising particles of at least one compound selected from the group consisting of calcium oxide, calcium hydroxide, strontium oxide and strontium hydroxide, and particles of metal sulfate.
  • the amount of the metal sulfate dissolved in 100 g of water is 0.5 g or more at 5 ° C.
  • grains of the said compound is 17 micrometers or less, and the average particle diameter of the particle
  • the content of the particles of the compound is 0.10 to 50.0% by mass based on the total solid content of the paint, and the content of the particles of the metal sulfate is the total solid content of the paint.
  • the steel material or the like coated with the above-mentioned paint has high corrosion resistance by the reaction between the paint component, the steel material and the substance in the corrosive environment to form an anticorrosive compound layer in an acidic environment or a severe corrosive environment including chloride.
  • the said coating material further contains a coupling agent, and it is preferable that content of the said coupling agent is 10.0 mass% or less on the basis of the total solid of the said coating material.
  • the coating material contains the coupling agent, the adhesion between the compound particles constituting the anticorrosion compound layer is improved, and higher corrosion resistance can be easily obtained.
  • the said coating material further contains a phosphoric acid, and it is preferable that content of the said phosphoric acid is 10.0 mass% or less on the basis of the total solid of the said coating material.
  • the adhesion between the coating film and the steel material can be improved.
  • the paint preferably further includes at least one metal powder selected from the group consisting of aluminum powder, zinc powder, and alloy powder containing aluminum and zinc, and the content of the metal powder is preferably It is preferable that it is 80.0 mass% or less on the basis of a total solid.
  • the metal powder in the coating film can support the sacrificial corrosion preventing action of the plating metal in a plated steel material or the like in which the plating metal has already been worn by corrosion or the like.
  • the said coating material further contains a cellulose nanofiber, and it is preferable that content of the said cellulose nanofiber is 5.0 mass% or less on the basis of the total solid of the said coating material.
  • the above-mentioned paint contains cellulose nanofibers, it is possible to refine the crystal particles constituting the anticorrosion compound layer to enhance the cohesion and to further improve the corrosion resistance of the steel material.
  • the present invention also provides a coated steel material comprising a steel material and a coating film formed on the surface of the steel material.
  • the coating film includes particles of at least one compound selected from the group consisting of calcium oxide, calcium hydroxide, strontium oxide, and strontium hydroxide, and particles of metal sulfate.
  • the amount of the metal sulfate dissolved in 100 g of water is 0.5 g or more at 5 ° C., the average particle diameter of the particles of the compound is 17 ⁇ m or less, and the average particle diameter of the particles of the metal sulfate is 17 ⁇ m or less .
  • the content of the particles of the compound is 0.10 to 50.0% by mass based on the total amount of the coating, and the content of the particles of the metal sulfate is based on the total amount of the coating. It is 0.05 to 30.0% by mass.
  • the coated steel material has high corrosion resistance in an acidic environment or a severe corrosive environment including chloride.
  • the coating film preferably has a moisture permeability of 300 g / (m 2 ⁇ 24 h) or less at a dry film thickness of 100 ⁇ m.
  • the coating film has the above moisture permeability, calcium oxide, calcium hydroxide, strontium oxide, strontium hydroxide, metal sulfate and the like are less likely to flow out in a corrosive environment, effectively forming the anticorrosive compound layer. It becomes easy to be served.
  • the coated steel material preferably further comprises a top coat film provided on the coating film, and the top coat film has a moisture permeability of 300 g / (m 2 ⁇ 24 h) or less at a dry film thickness of 100 ⁇ m. Is preferred.
  • the coated steel material further includes the above-described top coat, design properties can be imparted to the steel material etc., and the anticorrosion effect by the anticorrosion compound layer can be assisted, and the corrosion resistance of the steel material can be further improved. It becomes.
  • a coating material capable of providing high corrosion resistance to a steel material or the like in an acidic environment or a severe corrosive environment containing a chloride, and a coated steel material obtained using the same.
  • the paint according to the present embodiment includes particles of at least one compound selected from the group consisting of calcium oxide, calcium hydroxide, strontium oxide, and strontium hydroxide, and particles of metal sulfate.
  • a corrosion reaction forms a compound layer such as an oxide called so-called rust on the surface. If this compound layer is stable, dense and corrosion resistant, the corrosion resistance of the steel material is ensured, but usually this compound layer is highly likely to cause a phase change, and it contains voids etc. It is too low to sufficiently suppress the permeation of water and oxygen present in the external corrosive environment to the surface of the underlying metal such as various corrosive substances.
  • transmitted the coating film from the environment and was supplied in the initial stage which exposed coating steel materials under corrosion environment
  • Metal ions such as iron from steel materials and calcium ions, strontium ions, sulfate ions and metal ions are supplied from the coating film by oxygen and various corrosive substances, and between the steel material and the coating film or inside the coating film
  • An anticorrosion compound layer is formed which contains complex oxides of metals such as iron, calcium and strontium, and sulfates of metals such as calcium and strontium.
  • the anticorrosive compound layer obtained by the paint of the present embodiment is compact and has high stability.
  • the generated anticorrosion compound layer can suppress excessive permeation of water, oxygen and various corrosive substances present in the external corrosive environment into the steel material (barrier effect).
  • the steel material (corrosion-resistant steel structure) in which the said anticorrosion compound layer was formed has the outstanding corrosion resistance not only in general corrosion environment but in severe corrosive environment containing an acidic environment or a chloride. Therefore, the paint according to the present embodiment can also be said to be a paint for anticorrosive compound layer formation.
  • the coating material which concerns on this embodiment can also be mixed and used with general coating materials other than the coating material which concerns on this embodiment, for example, an epoxy resin coating material etc.
  • general coating materials other than the coating material which concerns on this embodiment, for example, an epoxy resin coating material etc.
  • Calcium oxide and calcium hydroxide react with water in a corrosive environment to supply calcium ions.
  • strontium oxide and strontium hydroxide hereinafter sometimes referred to as a strontium compound
  • strontium oxide and strontium hydroxide react with water in a corrosive environment to supply strontium ions.
  • the calcium ion and the strontium ion can significantly enhance the corrosion resistance of the iron rust layer which is the basis of the anticorrosion compound layer. That is, when an iron rust layer is formed from iron ions, calcium ions and strontium ions coagulate an octahedral or tetrahedral unit consisting of Fe-O-H forming iron rust to form crystals of the anticorrosive compound layer. It can be miniaturized and made extremely precise.
  • the calcium ion and the strontium ion further react with the sulfate ion generated by the dissociation of the metal sulfate to form calcium sulfate and strontium sulfate which are poorly soluble in water.
  • the calcium sulfate and strontium sulfate fill the voids of the anticorrosion compound layer formed at the interface between the coating film and the steel material by corrosion reaction in parallel with the formation of calcium sulfate and strontium sulfate, respectively, thereby densifying the anticorrosion compound layer. be able to.
  • the average particle diameter of the particles of at least one compound selected from the group consisting of calcium oxide, calcium hydroxide, strontium oxide, and strontium hydroxide is 17 ⁇ m or less.
  • the average particle size of the particles of the calcium compound or the strontium compound is 17 ⁇ m or less, calcium ions or strontium ions are supplied at a sufficient rate with respect to the formation rate of iron rust, and the above-mentioned calcium ions or strontium ions are used. It becomes easy to get the effect.
  • the average particle size is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the paint may contain only particles of any one compound selected from the group consisting of calcium oxide, calcium hydroxide, strontium oxide and strontium hydroxide as particles of at least one compound selected from the above group It may well include particles of a plurality of compounds selected from the above group.
  • the "average particle size" of particles is an average particle size measured as follows, unless otherwise specified. First, a paint containing each particle is applied to a polished steel plate so as to form a dry coating of 100 ⁇ m or more, and then dried. The cross section of the coating after drying is observed by SEM (Scanning Electron Microscopy) -EDS (Energy Dispersive X-ray Spectroscopy). Based on the results of elemental analysis (composition analysis) by EDS, each particle observed in the image is classified into particles to be measured and particles other than the object to be measured. Subsequently, a total of 200 unidirectional maximum diameters of particles to be measured are obtained, and the arithmetic average is taken as an average particle diameter.
  • SEM Sccanning Electron Microscopy
  • EDS Electronic X-ray Spectroscopy
  • the “particles of at least one compound selected from the group consisting of calcium oxide, calcium hydroxide, strontium oxide, and strontium hydroxide” is a particle composed of a single compound of four compounds. It may be present, or it may be a particle composed of a plurality of compounds out of four compounds. Therefore, if two or more areas of the above four compositions are in contact in the image, these areas are added together and recognized as one particle. In addition, if regions of one of the four compounds are in contact with each other, these are also added together and recognized as one particle.
  • the total content of particles of at least one compound selected from the group consisting of calcium oxide, calcium hydroxide, strontium oxide, and strontium hydroxide is based on the total solids of the above-mentioned paint, It is 0.10 to 50.0 mass%.
  • the content of particles of the above-mentioned compound in the paint is 0.10 mass% or more, the above-mentioned effects are easily exhibited.
  • the content of the particles of the above-mentioned compound in the paint is 50.0 mass% or less, the excessive rise in pH at the initial stage of corrosion is suppressed, and the above-mentioned effects are easily exhibited. Film peeling can be suppressed.
  • the content is preferably 1.0 to 45.0% by mass, and more preferably 10.0 to 45.0% by mass.
  • the metal sulfate contained in the paint according to the present embodiment is water soluble, and the amount of the metal sulfate dissolved in 100 g of water is 0.5 g or more at 5 ° C.
  • dissociation of metal sulfate may occur when water is supplied by rainfall or condensation even in the winter season when the temperature is low. That is, the metal sulfate dissociates into metal ions and sulfate ions at a constant concentration when water is supplied.
  • the dissociated sulfate ions promote the dissolution of iron in the steel at the initial stage of exposure to the corrosive environment, contribute to the early formation of the anticorrosive compound layer, and at the same time the thermodynamic stability of the formed iron oxide It is possible to prevent the iron oxide from acting as an oxidizing agent when being exposed to a corrosive environment after formation of the anticorrosion compound layer.
  • the sulfate ion reacts with the calcium ion dissociated from the above-mentioned calcium compound or the strontium ion dissociated from the strontium compound to form a hardly soluble calcium or strontium sulfate in water.
  • the formed calcium sulfate or strontium sulfate can be filled in the voids of the anticorrosion compound layer to densify the same and improve the anticorrosion property of the anticorrosion compound layer.
  • the dissociated metal ions are adsorbed to the anticorrosive compound layer while forming complex ions with the coexistent anions, and the ion selective permeability is imparted to the anticorrosive compound layer, thereby suppressing the permeation of the corrosive anion to the steel material.
  • the metal ion oxide is generated to significantly enhance the environmental blocking effect of the anticorrosion compound layer.
  • the dissociated sulfate ion forms a sulfate with the calcium ion supplied from the calcium compound or the strontium ion supplied from the strontium compound, as described above.
  • metal sulfate examples include magnesium sulfate, aluminum sulfate, nickel sulfate, iron sulfate, cobalt sulfate, copper sulfate, zinc sulfate, tin sulfate and chromium sulfate.
  • the metal sulfate is preferably at least one compound selected from the group consisting of aluminum sulfate, nickel sulfate and magnesium sulfate.
  • the metal sulfate is present as particles, and its average particle size is 17 ⁇ m or less.
  • the average particle size of the metal sulfate particles is 17 ⁇ m or less, sulfate ions and metal ions are supplied at a rate sufficient to the formation rate of iron rust, and the above-mentioned effects of the sulfate ions and metal ions are It becomes easy to obtain.
  • the average particle size is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the definition of the average particle size of the metal sulfate particles is the same as described above.
  • the number of metal sulfates to be measured becomes a plurality.
  • the average particle size of the particles of at least one compound selected from the group consisting of calcium oxide, calcium hydroxide, strontium oxide and strontium hydroxide is 17 ⁇ m or less, and the average of the particles of the metal sulfate described above Since the particle size is 17 ⁇ m or less, the formation rates of calcium ion, strontium ion, sulfate ion and metal ion can be balanced with each other, and electricity having the possibility of forming a large defect in the anticorrosive compound layer can be obtained. Since it becomes difficult to form a chemical local battery, the above-mentioned effects of calcium ions, strontium ions, sulfate ions and metal ions can be sufficiently obtained. When the above-mentioned average particle diameter is not 17 ⁇ m or less, as a result, the defects of the anticorrosive compound layer increase, and the anticorrosion in a severe corrosive environment can not be secured.
  • the content of the metal sulfate particles is, for example, 0.05 to 30.0% by mass based on the total solid content of the paint.
  • the content is 0.05% by mass or more, the above-described effect exhibited by the metal sulfate is easily obtained.
  • the content is 30.0% by mass or less, the coating film becomes brittle, and peeling of the coating film can be suppressed before the effect of the present invention is obtained.
  • the content is preferably 1.5 to 25.0% by mass, and more preferably 3.0 to 22.0% by mass.
  • the ratio of the content of metal sulfate particles to the total content of calcium compound and strontium compound particles is, for example, 0.1 to 300.0. And preferably 0.3 to 15.0, more preferably 0.5 to 5.0.
  • the paint according to the present embodiment may further contain phosphoric acid.
  • Phosphoric acid has the effect of improving the adhesion between the coating film and the steel material.
  • the phosphoric acid in a coating film dissociates into a hydrogen ion and a phosphate ion, when it touches water.
  • iron phosphate can be generated by the reaction between iron ions eluted from the steel material and phosphoric acid, and the anticorrosion compound layer can be further densified.
  • the dissociated phosphate ions react with calcium ions or strontium ions to form calcium phosphate or strontium phosphate which is hardly soluble in water, and the environmental barrier properties of the anticorrosion compound layer can be improved.
  • the content of phosphoric acid can be, for example, 10.0% by mass or less based on the total solid content of the paint.
  • the content is 10.0% by mass or less, the densification of the anticorrosive compound layer by the calcium compound or the strontium compound becomes dominant over the formation of iron phosphate, and the steel material needs to be corroded at the early stage of corrosive environment exposure It is possible to suppress acceleration above.
  • the above content is preferably 0.3 to 10.0% by mass, more preferably 0.6 to 10.0% by mass, and still more preferably 1.0 to 10.0% by mass.
  • the paint according to the present embodiment may further contain at least one metal powder selected from the group consisting of aluminum powder, zinc powder, and alloy powder containing aluminum and zinc.
  • the constituent elements of these metal powders can be the same as the constituent elements of the plated metal used for the plating of steel materials.
  • the metal powder in the coating film can support the sacrificial corrosion preventing action of the plating metal in a plated steel material or the like in which the plating metal has already been worn by corrosion or the like.
  • the said metal powder in a coating film ionizes by a corrosion reaction, and supplies a metal ion. Then, the supplied metal ions are oxidized together with calcium ions, strontium ions and iron ions to form an anticorrosive composite oxide, which contributes to the formation of the anticorrosive compound layer.
  • the content of the metal powder can be, for example, 80.0% by mass or less based on the total solid content of the paint.
  • the content is 80.0 mass% or less, generation
  • content of metal powder may exceed 80.0 mass%.
  • the lower limit of the content when metal powder is contained can be 5 mass%.
  • the paint according to the present embodiment may further contain a coupling agent.
  • a coupling agent When the above-mentioned paint contains a coupling agent, the adhesion between the compound particles constituting the anticorrosion compound layer can be improved, and the corrosion resistance of the steel material can be further improved.
  • the content of the coupling agent can be, for example, 10.0% by mass or less based on the total solid content of the paint.
  • the content of the coupling agent may exceed 10.0% by mass as long as a coating film design capable of avoiding the saturation of the effect of improving the adhesion can be realized separately.
  • the lower limit of the content in the case of containing the coupling agent can be 0.1 mass%.
  • the paint according to the present embodiment may further contain cellulose nanofibers.
  • cellulose nanofibers When the above-mentioned paint contains cellulose nanofibers, it is possible to refine the crystal particles constituting the anticorrosion compound layer to enhance the cohesion and to further improve the corrosion resistance of the steel material.
  • the content of the cellulose nanofibers can be, for example, 5.0% by mass or less based on the total solid content of the paint.
  • the content is 5.0% by mass or less, the effect of improving the cohesiveness does not saturate with respect to the increase of the content, and it tends to be able to be obtained according to the increase of the content.
  • the said content is 5.0 mass% or less, there exists a tendency which can suppress that the viscosity of the said coating material becomes high too much, and can prevent the fall of coating efficiency.
  • the content of the cellulose nanofibers may exceed 5.0% by mass as long as a coating film design capable of avoiding the saturation of the effect of the aggregation can be separately realized.
  • the lower limit of the content in the case of containing cellulose nanofibers can be 0.05 mass%.
  • the paint according to the present embodiment can further contain a resin.
  • the resin is not particularly limited, and vinyl butyral resin (polyvinyl butyral resin etc.), epoxy resin, modified epoxy resin, acrylic resin, urethane resin, nitrocellulose resin, vinyl resin (polyvinyl chloride, polyvinyl acetate, and polyvinyl alcohol) And the like), phthalic acid resin, melamine resin, and fluorine resin.
  • These resins may be thermoplastic resins or thermosetting resins.
  • the paint may further contain a curing agent as needed, and the paint is usually cured during and after drying.
  • the weight average molecular weight of the thermosetting resin is not particularly limited, but is about 200 to 20000.
  • the weight average molecular weight of the thermoplastic resin is not particularly limited, but is about 10,000 to 5,000,000. Since the said coating material contains resin, after apply
  • the lower limit value of the content of the resin in the paint may be, for example, 3.0% by mass, or 5.0% by mass, based on the total solid content of the paint, or 10.0% by mass. 20 mass% may be sufficient.
  • the upper limit value of the resin content in the paint may be, for example, 95.0% by mass, 90.0% by mass, or 70.0% by mass, based on the total solid content of the paint. It may be 50.0 mass%.
  • the content of the resin is 95.0% by mass or less, the anticorrosive compound layer tends to be easily formed on the steel material.
  • the paint according to the present embodiment contains, as necessary, additives such as a thixotropic agent, a dispersant, and an antioxidant, in addition to other general color pigments, an extender pigment, a rust preventive pigment, and a special function pigment. Can be included.
  • the paint may contain anti-corrosion pigments to control the corrosion resistance when the corrosive environment is severe, but its content is determined by the total solids content of the paint, in order not to impart excessive corrosion resistance to the corrosion-resistant steel structure. 30.0 mass% or less, 20.0 mass% or less, or 10.0 mass% or less.
  • the average particle diameter of the particulate material other than the calcium compound, the strontium compound and the metal sulfate contained in the paint can be 100 ⁇ m or less, preferably 30 ⁇ m or less.
  • the paint according to the present embodiment can further contain a solvent.
  • Non-aqueous solvents such as aromatic solvents such as xylene and toluene, alcohol solvents having 3 or more carbon atoms such as isopropyl alcohol and normal butanol, and esters such as ethyl acetate; water, methyl alcohol and ethyl alcohol And water-based solvents such as
  • the resin may be a resin that dissolves in the solvent, may be a resin that dissolves in a non-aqueous solvent, or may be a resin that dissolves in an aqueous solvent.
  • the viscosity of the paint is measured by a B-type viscometer at 20.degree.
  • the viscosity of the above-mentioned paint is appropriately selected according to the coating method, and can be, for example, 200 to 1000 cps.
  • the content of the solvent in the paint can be adjusted so that the viscosity of the paint is in the above range.
  • FIG. 1 is a cross-sectional view showing a coated steel material according to an embodiment of the present invention and a corrosion resistant steel structure obtained therefrom, wherein (a) shows a steel material 10 and (b) shows a surface of the steel material 10 and the steel material 10 The coated steel material 100 provided with the coating film 20 provided in (c) shows the corrosion-resistant steel structure 200 in which the anticorrosive compound layer 30 was formed between the steel materials 10 and the coating film 20.
  • FIG. 1 is a cross-sectional view showing a coated steel material according to an embodiment of the present invention and a corrosion resistant steel structure obtained therefrom, wherein (a) shows a steel material 10 and (b) shows a surface of the steel material 10 and the steel material 10 The coated steel material 100 provided with the coating film 20 provided in (c) shows the corrosion-resistant steel structure 200 in which the anticorrosive compound layer 30 was formed between the steel materials 10 and the coating film 20.
  • FIG. 1 is a cross-sectional view showing a coated steel material according to an embodiment of the present invention and
  • the steel type of the steel material 10 shown in (a) of FIG. 1 is not particularly limited, and may be an ordinary steel material, a low alloy steel material, a high alloy steel material such as stainless steel, or the like It may be steel.
  • the steel material may not have a rust layer or an organic layer or an inorganic layer on the surface, and may have a rust layer or an organic layer or an inorganic layer.
  • the surface of the steel material 10 may be polished by shot blasting or a power tool before application, and if a rust layer is formed on the surface, rust that can be easily removed by a wire brush or the like may be removed. Moreover, when steel materials have a rust layer, an organic layer, or an inorganic layer on the surface, these layers need not be peeled off, and a coating film can be provided on the surface of steel materials including these layers.
  • the coated steel material 100 provided with the coating film 20 of (b) of FIG. 1 can be obtained by applying the above-mentioned paint to the surface of the steel material 10 prepared in (a) and drying the paint as needed. it can. Therefore, the composition of the coating film 20 can be identical to the composition of the solid content in the paint. In addition, the average particle size of the particulate material in the coating film 20 can be the same as the average particle size in the above-mentioned paint. That is, the coating film 20 includes particles of at least one compound selected from the group consisting of calcium oxide, calcium hydroxide, strontium oxide, and strontium hydroxide, and particles of metal sulfate.
  • the amount of the metal sulfate dissolved in 100 g of water is 0.5 g or more at 5 ° C.
  • the average particle size of the particles of at least one compound selected from the group consisting of calcium oxide, calcium hydroxide, strontium oxide and strontium hydroxide is 17 ⁇ m or less, and the average particle size of the metal sulfate particles is 17 ⁇ m or less.
  • the content of the particles of the compound is 0.10 to 50.0% by mass based on the total amount of the coating, and the content of the particles of the metal sulfate is based on the total amount of the coating. It is 0.05 to 30.0% by mass.
  • Examples of the coating method include air spray, airless spray, brush coating and roller coating.
  • drying of the said coating material is performed by natural drying in air of normal temperature (25 degreeC) normal pressure (1 atm), etc., for example.
  • the drying time varies depending on the drying form, it is usually about 30 minutes to 6 hours and is selected to such an extent that a practical coating strength can be obtained.
  • the paint can be applied at any place.
  • coating at the site where the coated steel material is installed is possible, it is possible to cope even after processing such as cutting and welding of the steel material at the site.
  • the thickness of the coating film 20 may be 1 to 1000 ⁇ m.
  • each component in the coating is sufficiently retained on the steel material, and when the coated steel material is exposed to a corrosive environment, the steel material is formed against the formation of the anticorrosive compound layer 30 There is a tendency that only the corrosion of Therefore, a sufficient barrier effect can be easily obtained for the steel material by the anticorrosion compound layer 30.
  • the corrosion protection compound layer 30 can be formed by preventing excessive corrosion due to permeation of chloride ions.
  • the thickness of the above coating film is 1000 ⁇ m or less, but also the coating moment when a bending moment is generated in the coating film due to stress generated by the steel material of the base material under any influence. It is possible to suppress cracking of the film 20 or peeling from the surface of the steel material.
  • the lower limit of the thickness of the coating film 20 may be 3 ⁇ m, 5 ⁇ m, or 10 ⁇ m.
  • the upper limit of the thickness of the coating film 20 may be 750 ⁇ m or 500 ⁇ m.
  • the coating film 20 preferably has a moisture permeability of 300 g / (m 2 ⁇ 24 h) or less and more preferably 200 g / (m 2 ⁇ 24 h) or less at a dry film thickness of 100 ⁇ m.
  • the moisture permeability refers to the amount of water vapor passing through a film-like substance of a unit area in a fixed time, and with the film-like substance as a boundary, one air is kept dry by 90% relative humidity and the other air by a dehumidifying agent. The amount of water vapor passing through the boundary in 24 hours is converted to 1 m 2 of the film-like substance.
  • the coating film 20 has a moisture permeability of 300 g / (m 2 ⁇ 24 h) or less to accelerate the dissociation of calcium oxide, calcium hydroxide, strontium oxide, strontium hydroxide, metal sulfate and the like in a corrosive environment. It is possible to suppress these outflows to the outside. As a result, calcium oxide, calcium hydroxide, strontium oxide, strontium hydroxide and metal sulfate in the coating film 20 are easily provided to the formation of the anticorrosive compound layer 30.
  • particles of calcium oxide, calcium hydroxide, strontium oxide, strontium hydroxide and metal sulfate have a small average particle diameter of 17 ⁇ m or less, they are easily dissociated in a corrosive environment, and the anticorrosive compound layer It can contribute to early formation.
  • the dissociation in the corrosive environment is relatively easy to occur, the moisture permeability of the coating film 20 is low from the viewpoint that the amount of supplied water is not excessive at the initial stage of exposure to the corrosive environment. preferable.
  • the moisture permeability of the coating film 20 is too low, the reaction (dissociation etc.) of calcium oxide, calcium hydroxide, strontium oxide, strontium hydroxide and metal sulfate will be delayed, which itself is anticorrosive in severe corrosive environment There is no problem from the viewpoint of securing the If the moisture permeability of the coating film is not zero, water or the like slightly infiltrates, and the formation of the anticorrosive compound layer accompanied by corrosion proceeds. Therefore, even if the moisture permeability of the coating film 20 is low, if it is not zero, the effect of the present invention can be obtained.
  • the coated steel material 100 may further include a top coat film provided on the coat film 20.
  • the top coat film preferably has a moisture permeability of 300 g / (m 2 ⁇ 24 h) or less and a moisture permeability of 200 g / (m 2 ⁇ 24 h) or less at a dry film thickness of 100 ⁇ m.
  • the moisture permeability refers to the amount of water vapor passing through a film-like substance of a unit area in a fixed time, and with the film-like substance as a boundary, one air is kept dry by 90% relative humidity and the other air by a dehumidifying agent.
  • the amount of water vapor passing through the boundary in 24 hours is converted to 1 m 2 of the film-like substance.
  • the moisture permeability of the topcoat film may be 20 g / (m 2 ⁇ 24 h) or more at a dry film thickness of 100 ⁇ m.
  • the moisture permeability of the top coat film is 20 g / (m 2 ⁇ 24 h) or more, the water necessary for the formation of the anticorrosion compound layer can be easily supplied early between the steel material 10 and the coating film 20 to impart corrosion resistance.
  • the resin paint for forming the top coat film may be polyethylene resin, epoxy resin, polyvinyl butyral resin, polyvinyl alcohol resin, or a mixture of these.
  • the moisture permeability of the top coat film can be controlled within a desired range by selecting or mixing the resin used for the resin paint.
  • the moisture permeability of polyethylene resin is about 5 to 20 g / (m 2 ⁇ 24 h)
  • the moisture permeability of epoxy resin is about 20 to 40 g / (m 2 ⁇ 24 h)
  • the moisture permeability of polyvinyl butyral resin is about It is 100 to 200 g / (m 2 ⁇ 24 h)
  • the moisture permeability of the polyvinyl alcohol resin is about 200 to 400 g / (m 2 ⁇ 24 h).
  • the top coat film is, for example, 10 to 300 ⁇ m, preferably 25 to 200 ⁇ m, and more preferably 25 to 150 ⁇ m.
  • the thickness of the topcoat film may be 30 ⁇ m or more, and may be 50 ⁇ m or more.
  • a top coat film is a protective film for protecting steel materials etc. together with the said coating film.
  • the protective film comprises the coating film and a top-coating film provided on the coating film.
  • the corrosion resistant steel structure 200 includes a steel material 10, a coating film 20, and a corrosion protection compound layer 30 formed between the steel material 10 and the coating film.
  • a corrosion protection compound layer 30 formed between the steel material 10 and the coating film.
  • a suitable exposure environment of the coated steel material 100 can be a water-containing atmosphere capable of providing moisture to the coated steel material 100, and the exposure is, for example, under outdoor environment or indoor environment, such as hydrochloric acid. an acidic environment, sea salt flying environment, or may be performed in air pollutants flying environment such as SO x or NO x. Further, as a suitable exposure condition of the coated steel material 100, for example, exposure to the outside for about 1 to 30 days can be mentioned.
  • the corrosion resistant steel structure 200 is provided with the anticorrosive compound layer 30, excessive permeation of water, oxygen and various corrosive substances present in the external corrosive environment into the steel can be suppressed (barrier effect), It has excellent corrosion resistance not only in a general corrosive environment but also in an acidic environment or a severe corrosive environment including chloride. After the formation of the anticorrosive compound layer 30, the coating film 20 may be peeled off.
  • the thickness of the anticorrosive compound layer 30 may be about 0.5 to 50 ⁇ m. When the thickness of the anticorrosion compound layer 30 is 0.5 ⁇ m or more, the corrosion resistance of the steel material is easily obtained.
  • This anticorrosion compound layer exerts its effect not only in a general corrosive environment but also in an acidic environment or a severe corrosive environment containing chloride.
  • the term “acidic environment” or the severe corrosive environment containing chloride referred to here means a low pH environment (for example, pH 4.0 or less) or a natural atmospheric corrosive environment (general corrosive environment on the surface of various steels). For example, an environment where it is assumed that corrosion of steel materials is significantly accelerated, such as being present at a concentration higher than) (for example, on the ground where seawater in the immediate vicinity of the sea flies directly).
  • a plated steel material 14 may be used instead of the steel material 10.
  • the plated steel material 14 has on the surface of the steel material 10 a plated layer 12 of a metal having an anticorrosion effect, for example, a metal such as aluminum, zinc and alloys thereof.
  • the coated steel material 100 includes the plated steel material 14 and the coating film 20 formed on the surface of the plated steel material 14.
  • the plated steel material 14 include hot-dip galvanized steel materials.
  • the corrosion resistant steel structure 200 includes the plated steel 14, the coated film 20, the plated steel 14 and the coated film 20. And an anticorrosion compound layer 30 formed between or within the coating film 20.
  • the said coating material is apply
  • the formation of zinc ions or zinc oxide due to corrosion of a part of zinc etc. in the plated layer 12 contributes to the formation of the anticorrosive compound layer 30.
  • Example 1 Preparation of paint> Raw material particles of calcium oxide, strontium oxide, aluminum sulfate, nickel sulfate, and magnesium sulfate were prepared, and each particle was subjected to a process of grinding / disintegrating in a dry jet mill to reduce the particle size.
  • Example 1 3 parts by mass of calcium oxide particles after treatment, 3 parts by mass of strontium oxide particles after treatment, 2 parts by mass of aluminum sulfate particles after treatment, 2 parts by mass of particles of nickel sulfate after treatment, 2 parts by mass of magnesium sulfate after treatment Parts, 10 parts by mass of an extender / coloring pigment, and 78 parts by mass of a mixture of an epoxy resin and a polyaminoamide resin (resin Y shown in Table 3) in an appropriate amount such that the viscosity of the coating is 200 to 1000 cps at 20 ° C.
  • the paint of Example 1 was obtained by dispersing in a bead mill with xylene, toluene and isopropyl alcohol.
  • constitution and color pigment are barium sulfate and calcium carbonate as an extender pigment, and bengala, carbon (inorganic pigment) and phthalocyanine blue (organic pigment as a color pigment). Pigments, each containing equal parts by mass.
  • the composition of the solid content of the paint is shown in Table 4.
  • Test pieces (I) shown in the following Table 1 having dimensions of 30 ⁇ 25 ⁇ 5 mm were prepared.
  • Table 1 shows the chemical composition of the steel used in the corrosion test and the presence or absence of zinc plating. All units of numerical values in Table 1 are% by mass, and chemical components other than those described in Table 1 are iron (Fe).
  • Pretreatment ⁇ shown in Table 2 below was performed on the surface of the test piece (I), and the obtained test piece having a clean surface was used as a test piece (I ⁇ ).
  • Test material A in Table 4 means the above-mentioned test piece (I ⁇ ).
  • the paint obtained was applied to the surface of the test piece (I ⁇ ) after the pretreatment by an air spray method. Then, the coated steel material of Example 1 was obtained by drying the test material after application in air at normal temperature (25 ° C.) for 7 days in accordance with a common coating film test method. The thickness of the coating film formed from the paint was 25 ⁇ m.
  • Examples and Comparative Examples 2 to 110, Examples and Comparative Examples 121 to 150, and Comparative Examples 161 to 170 are the same as Example 1 except that the composition of the paint is changed as described in Tables 4 to 14, 16 to 18 and 20. Paints of ⁇ 150 and Comparative Examples 161-166 were obtained.
  • the paints of Comparative Examples 161 to 166 the commercially available organic zinc rich paints specified in JIS K 5553 were used. The amount of solvent in the paint was suitably adjusted so that the viscosity of the paint at 20 ° C. using a B-type viscometer would be 200 to 1000 cps. In Comparative Examples 167 to 170, no paint was applied.
  • Examples and Comparative Examples 2 to 110, Examples and Comparative Examples 121 to 150, and Comparative Examples 161 to 170 test pieces of steel materials, pretreatment methods, and thicknesses of coating films are shown in Tables 4 to 14, Examples and Comparative Examples 2 to 110, Examples and Comparative Examples 121 to 150, and Comparative Examples 161 to 170 are the same as Example 1 except that they are changed as described in Tables 16 to 18 and Table 20. Coated steel was obtained.
  • the average particle diameter of the particles may be grinding the particles in a powdery state with a dry jet mill, dispersing in a paint with a 3-roll mill or a bead mill, and changing the time of the above grinding or dispersion alone or It adjusted by performing in combination.
  • Examples 111 to 120 and Examples 151 to 160 Coatings of Examples 111 to 120 and Examples 151 to 160 were obtained in the same manner as in Example 1 except that the composition of the coating was changed as described in Tables 15 and 19. The amount of solvent in the paint was suitably adjusted so that the viscosity of the paint at 20 ° C. using a B-type viscometer was 200 to 1000 cps. Furthermore, in Examples 111 to 120 and Examples 151 to 160, the test pieces of the steel material, the pretreatment method, and the thickness of the coating film are changed as described in Table 15 and Table 19 to form a coating film.
  • Example 1 Same as Example 1 except that a top coat film formed by applying a top coat on this coat was formed to have the thickness and the moisture permeability described in Tables 15 and 19
  • the coated steel materials of Examples 111 to 120 and Examples 151 to 160 were obtained.
  • the average particle diameter of the particles may be grinding the particles in a powdery state with a dry jet mill, dispersing in a paint with a 3-roll mill or bead mill, and changing the time of the above grinding or dispersion alone or It adjusted by performing in combination.
  • the moisture permeability of top coat film was adjusted by using polyethylene resin, an epoxy resin, polyvinyl butyral resin, and polyvinyl alcohol resin individually or in mixture as top coat paints.
  • the top coat having a thickness of 100 ⁇ m is prepared for measuring the moisture permeability using the same top coat as in each of the Examples and Comparative Examples, and the condition B (temperature 40) of JIS Z 0208 (cup method) C., relative humidity 90%).
  • Examples 171 to 178 Paints and coated steel materials of Examples 171 to 174 were obtained in the same manner as in Example 16 except that a coating film was formed so that the moisture permeability would be as described in Table 21.
  • the paint and the coated steel materials of Examples 175 to 178 were obtained in the same manner as in Example 36 except that the coating film was formed so that the moisture permeability would be as described in Table 21.
  • the moisture permeability of the coating film was adjusted by using an appropriate mixture of epoxy resin, polyvinyl butyral resin, urethane resin, polyethylene resin, and cellulose diacetate resin as the resin in the preparation of the coating.
  • the moisture permeability of the coating film was measured by the following two methods (a method using a cellulose triacetate film and a method using a release paper).
  • the same paint as used in each example was applied onto a cellulose triacetate film and a release paper, respectively, and dried to form a 100 ⁇ m thick coating.
  • the coating film was mechanically peeled from the release paper to obtain a coating film for moisture permeability measurement.
  • 10 paint films for measuring moisture permeability and 10 laminates of the paint film and the cellulose triacetate film were obtained from the paint of each example.
  • the moisture permeability of the coating film was measured by the method according to Condition B of JIS Z 0208 (cup method).
  • a coating film for moisture permeability measurement, a laminate of the coating film and a cellulose triacetate film, and a cellulose triacetate film which is the same as that used in the preparation of the laminate were respectively attached to a screw cup containing a hygroscopic agent.
  • the laminate was placed so that the triacetic acid cellulose film was directed to the hygroscopic agent side.
  • the screw type cup after mounting was placed in a constant temperature and humidity layer with a temperature of 40 ° C. and a relative humidity of 90%, and the cup mass after 24 hours was measured.
  • the moisture permeability of the coating film when converted to a unit area was determined from the average value of the mass change of the ten moisture permeability measuring coatings.
  • the moisture permeability of the coating film was determined by subtracting the mass change of the cellulose triacetate film from the average value of the mass changes of 10 laminates of the coating and the cellulose triacetate film, and converting to a unit area. Since the difference of the moisture permeability measured between the method using a cellulose triacetate film and the method using a release paper was hardly recognized, the average value of both methods was made into the moisture permeability of the coating film.
  • Example and Comparative Examples 181 to 186 Coatings of Examples and Comparative Examples 181 to 186 were obtained in the same manner as in Example 1 except that the coating composition was changed as described in Table 22.
  • the amount of solvent in the paint was suitably adjusted so that the viscosity of the paint at 20 ° C. using a B-type viscometer was 200 to 1000 cps.
  • Example and Comparative Example 181 were carried out in the same manner as Example 1, except that the test piece of the steel material, the pretreatment method, and the thickness of the coating film were changed as described in Table 22 to form a coating film.
  • a coated steel of ⁇ 186 was obtained.
  • the adjustment of the average particle diameter of the particles in Comparative Examples 181, 183 and 185 was not particularly strictly performed.
  • the average particle diameter of the particles in Examples 182, 184 and 186 is as follows: The particles in the powder state are crushed by a dry jet mill, and dispersed in the paint with a three roll mill or bead mill for a longer time than Comparative Examples 181, 183 and 185. It adjusted by doing.
  • the coated steel materials of Examples and Comparative Examples 181 to 182 and 183 to 184 were respectively produced under the same conditions of paint solids and coating film compositions and test materials as Test Nos. 41 and 42 in JP-A-2001-234369. Yes, the coated steel materials of Examples and Comparative Examples 185 to 186 were prepared under the same coating solid content, coating composition and test material conditions as Example 91 of WO 2014/020665.
  • Test materials B to D together with the test material A are used as test materials for the coated steel materials of the example and the comparative examples 2 to 178.
  • a test material E is used as a test material for the coated steel materials of Examples 181 to 184
  • a test material F is used for the coated steel materials of Examples 185 to 186.
  • Test materials A to F in Examples and Comparative Examples 2 to 186 will be described as follows.
  • test pieces (I) to (IV) shown in the above Table 1 were prepared.
  • the pretreatment ⁇ shown in Table 2 was performed on the surface of the test piece (II), and the obtained test piece was used as a test piece (II ⁇ ).
  • the pretreatment ⁇ shown in Table 2 was performed on the surfaces of the test pieces (I) and (II), and the obtained test pieces were used as test pieces (I ⁇ ) and (II ⁇ ), respectively.
  • the pretreatment ⁇ shown in Table 2 was performed on the surface of the test piece (III), and the obtained test piece was used as a test piece (III ⁇ ).
  • the pretreatment ⁇ shown in Table 2 was performed on the surface of the test piece (IV), and the obtained test piece was used as a test piece (IV ⁇ ).
  • test material A described in the test material column of Tables 4 to 22 means the test piece (I ⁇ ) as described above.
  • Test material B means the above test piece (I ⁇ ).
  • the test material C means the above test piece (II ⁇ ).
  • the test material D means the above test piece (II ⁇ ).
  • the test material E means the above test piece (III ⁇ ).
  • the test material F means the above test piece (IV ⁇ ).
  • exposure to the atmosphere in the above pretreatment ⁇ is located 20 m from the shore looking west of Obama Bay in Obama City, Fukui Prefecture (North latitude 35 degrees 31 minutes 49.39 seconds, East longitude 135 degrees 45 minutes 4.69 seconds In the above, the exposure posture was horizontal.
  • the average annual airborne salt content of the exposed site is about 0.8 mg NaCl / 100 cm 2 / day, which is a corrosive environment strongly affected by sea salt airborne.
  • the meanings of the symbols in the resin column of Tables 4 to 22 are as shown in Table 3 below.
  • the example described as X in the column of resin shows that polyvinyl butyral resin of the same mass was used in place of the mixture of epoxy resin and polyaminoamide resin (resin Y) of Example 1 ing.
  • the average particle size of the zinc powder in Tables 4 to 22 is 4 ⁇ m, and the average particle size of the aluminum powder is 6 ⁇ m.
  • a silane coupling agent As the coupling agent, a silane coupling agent (Shin-Etsu Chemical Co., Ltd., trade name: KBM-403) is used, and as the cellulose nanofibers, cellulose nanofibers (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Reocrystal) are used. Using.
  • the average particle size of the particles of the calcium compound and the strontium compound and the average particle size of the particles of the metal sulfate were measured by the following method. That is, the paint obtained in Examples and Comparative Examples was applied on a polished steel plate so as to have a dry film thickness of 100 ⁇ m or more. The cross section of the coated film after drying was observed by SEM (Scanning Electron Microscopy) -EDS (Energy Dispersive X-ray Spectroscopy), and elemental analysis was performed. Based on the result of elemental analysis by SEM-EDS, particles to be measured and particles other than the particles were distinguished in the image. 200 particles to be measured were arbitrarily selected, and the maximum diameter in the fixed direction of each particle was measured. The arithmetic mean value of the maximum directional diameter of 200 particles was defined as the average particle diameter of the particles.
  • the coating film is removed from the coated steel material after the exposure test using a coating film release agent, and then The obtained steel material was removed by immersion in a mixed aqueous solution of diammonium citrate and a trace amount of corrosion inhibiting solution.
  • the amount of decrease in thickness of the test piece before and after the exposure test was determined.
  • the reduction amount of the said thickness is calculated
  • test piece (I ⁇ ) When the above test piece (I ⁇ ) is used as a test material, another test piece subjected to the pretreatment ⁇ is removed in the same manner as described above, and the mass of the removed test piece is the weight of the test piece before the exposure test. The amount of decrease in thickness of the steel was determined in the same manner as in the test piece (I ⁇ ) except that it was regarded as mass.
  • test piece (II ⁇ ) or test piece (II ⁇ ) shown in Table 1 When using the test piece (II ⁇ ) or test piece (II ⁇ ) shown in Table 1 as the test material, measure the thickness of the galvanized layer from observation of the cross section of the test piece before and after the exposure test, and compare the two. The reduction amount of the thickness (plate thickness) of the steel material before and after the exposure test (the reduction amount of the combined thickness of the zinc plating and the ordinary steel material to be the base) was determined. The evaluation results are shown in Tables 4 to 21.
  • the reduction in thickness of the test specimen is extremely small as compared to the comparative example.
  • the reduction in thickness is extremely large in Comparative Examples 167 to 170 where no coating is applied at all.
  • Comparative Examples 161 to 166 where the paint was applied corrosion was suppressed rather than no coating at all, but still a large reduction in thickness was shown. From these things, it is concluded that the paint according to the present invention can impart high corrosion resistance to steel materials even in an acidic environment or a severe corrosive environment containing chloride.
  • the calcium compound (Ca compound) and the strontium compound (Sr compound) are shown on the vertical axis of the reduction in thickness of the test pieces of the examples and comparative examples 1 to 80 shown in Tables 4 to 11 in FIGS.
  • a scatter diagram is shown in which the average particle diameter of the particles of the particle or the average particle diameter of the particles of the metal sulfate is taken on the horizontal axis.
  • the thickness reduction of the test piece can be confirmed to increase rapidly.
  • the corrosion environment of the above-mentioned corrosion test is quite severe conditions compared with the natural corrosion environment (general corrosion environment) which exposes steel materials to rain and sunshine directly near a beach.
  • the reason is that, for example, in natural corrosive environments such as near the coast, sea water hardly flies directly, and sea salt particles fly into steel materials, so corrosion is likely to progress, but sea salt that has been deposited due to rainfall This is because the particles are washed away.

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US16/651,599 US20200255952A1 (en) 2017-10-06 2018-09-21 Coating material and coated steel
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EP18864176.5A EP3693422A1 (en) 2017-10-06 2018-09-21 Coating material and coated steel
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